JPH0687860A - Hydroxyphenylpropionic acid ester having new crystalline structure - Google Patents
Hydroxyphenylpropionic acid ester having new crystalline structureInfo
- Publication number
- JPH0687860A JPH0687860A JP5089737A JP8973793A JPH0687860A JP H0687860 A JPH0687860 A JP H0687860A JP 5089737 A JP5089737 A JP 5089737A JP 8973793 A JP8973793 A JP 8973793A JP H0687860 A JPH0687860 A JP H0687860A
- Authority
- JP
- Japan
- Prior art keywords
- crystal
- solvent
- ray diffraction
- hydroxy
- acid ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な結晶構造を有す
るヒドロキシフェニルプロピオン酸エステルに関するも
のである。本発明で対象とする化合物は、化学名を３，
９−ビス〔２−｛３−（３−ｔ−ブチル−４−ヒドロキ
シ−５−メチルフェニル）プロピオニルオキシ｝−１，
１−ジメチルエチル〕−２，４，８，１０−テトラオキ
サスピロ〔５・５〕ウンデカンといい、下記の式（Ｉ）
で示される。以下、単にヒドロキシフェニルプロピオン
酸エステル、またはさらに単純に式（Ｉ）の化合物と呼
ぶことがある。TECHNICAL FIELD The present invention relates to a hydroxyphenylpropionic acid ester having a novel crystal structure. The compound of interest in the present invention has a chemical name of 3,
9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,
1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, which has the following formula (I)
Indicated by. Hereinafter, it may be simply referred to as hydroxyphenylpropionic acid ester, or more simply as a compound of formula (I).
【０００２】[0002]
【化１】 [Chemical 1]
【０００３】[0003]
【従来の技術】上記式（Ｉ）で示されるヒドロキシフェ
ニルプロピオン酸エステルは、特公平3-9134 号公報
（＝特開昭 59-25826 号公報）、特開昭 59-231089号公
報および特公平 3-64546号公報（＝特開昭 60-197747号
公報）に記載され、公知である。式（Ｉ）の化合物は、
ポリエチレンやポリプロピレンのようなポリオレフィ
ン、ポリスチレンや耐衝撃性ポリスチレン、ＡＢＳのよ
うなスチレン系合成樹脂、ポリアセタールやポリアミド
のようなエンジニアリングプラスチック、さらにはポリ
ウレタンなど、各種合成樹脂の加工時や使用時の熱、光
および酸素の作用による軟化、脆化、表面亀裂、変色な
どの劣化現象を防止するための安定剤として有用であ
る。2. Description of the Related Art The hydroxyphenylpropionic acid ester represented by the above formula (I) is disclosed in Japanese Patent Publication No. 3-9134 (= Japanese Patent Publication No. 59-25826), Japanese Patent Publication No. 59-231089 and Japanese Patent Publication No. It is described in JP-A-3-64546 (= JP-A-60-197747) and is publicly known. The compound of formula (I) is
Heat during processing and use of various synthetic resins such as polyolefins such as polyethylene and polypropylene, polystyrene and impact resistant polystyrene, styrene synthetic resins such as ABS, engineering plastics such as polyacetal and polyamide, and polyurethane. It is useful as a stabilizer for preventing deterioration phenomena such as softening, embrittlement, surface cracking, and discoloration due to the action of light and oxygen.
【０００４】この化合物は一般に、対応するヒドロキシ
フェニルプロピオン酸の低級アルキルエステルと３，９
−ビス（２−ヒドロキシ−１，１−ジメチルエチル）−
２，４，８，１０−テトラオキサスピロ〔５・５〕ウン
デカンとのエステル交換反応によって製造されている。This compound is generally 3,9 with the corresponding lower alkyl ester of hydroxyphenylpropionic acid.
-Bis (2-hydroxy-1,1-dimethylethyl)-
It is produced by a transesterification reaction with 2,4,8,10-tetraoxaspiro [5.5] undecane.
【０００５】そして、この化合物は結晶多形であること
が、特開昭 62-149679号公報および特開昭 62-149680号
公報に開示されており、従来次のような結晶形が知られ
ていた。It is disclosed in JP-A-62-149679 and JP-A-62-149680 that this compound has a polymorphic crystal form, and the following crystal form has been conventionally known. It was
【０００６】（ｉ） 特公平 3-64546号公報に記載の方
法によって得られ、融点範囲約４５〜５５℃のガラス状
物質である、いわゆるγ晶、（ii） 特開昭 62-149680
号公報記載の方法によって得られ、融点範囲約１０４〜
１０９℃の白色結晶である、いわゆるαβ晶、（iii)
特開昭 62-149679号公報記載の方法によって得られ、融
点範囲約１２４〜１２７℃の白色結晶である、いわゆる
δ晶。(I) A so-called γ crystal, which is a glass-like substance having a melting point range of about 45 to 55 ° C., obtained by the method described in Japanese Patent Publication No. 3-64546, and (ii) JP-A-62-149680.
And a melting point range of about 104-
So-called αβ crystal, which is a white crystal at 109 ° C., (iii)
A so-called δ crystal, which is a white crystal having a melting point range of about 124 to 127 ° C., obtained by the method described in JP-A-62-149679.
【０００７】γ晶は、反応によって得られた不純物を含
んだままの混合物や、カラムロクマトグラフィーなどに
より純度を向上させて精製したものを溶融し、これを溶
媒を用いずに急冷することによって得られ、その融点範
囲は約４５〜５５℃である。また、そのCu−Ｋα波長の
Ｘ線を用いたＸ線回折パターンは、図５に示すようなも
のとなる。The γ-crystal is obtained by melting a mixture containing impurities obtained by the reaction or purified by improving the purity by column chromatography, etc., and quenching it without using a solvent. The melting point range obtained is about 45-55 ° C. Moreover, the X-ray diffraction pattern using the X-rays of the Cu-Kα wavelength is as shown in FIG.
【０００８】αβ晶は、ｎ−ヘキサンやシクロヘキサン
などからの再結晶によって得られ、その融点範囲は約１
０４〜１０９℃である。例えば、式（Ｉ）のヒドロキシ
フェニルプロピオン酸エステルと類似の化学構造を有す
る３，９−ビス〔２−｛３−（３，５−ジ−ｔ−ブチル
−４−ヒドロキシフェニル）プロピオニルオキシ｝−
１，１−ジメチルエチル〕−２，４，８，１０−テトラ
オキサスピロ〔５・５〕ウンデカンの精製法として、特
公平 3-9134 号公報にはｎ−ヘキサンからの再結晶法が
記載されているが、この方法をそのまま式（Ｉ）の化合
物に適用した場合に、αβ晶が得られる。αβ晶を、Cu
−Ｋα波長のＸ線を用いたＸ線回折にかけると、図４の
ような回折パターンを示す。The αβ crystal is obtained by recrystallization from n-hexane or cyclohexane, and its melting point range is about 1
It is 04-109 degreeC. For example, 3,9-bis [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy}-having a chemical structure similar to the hydroxyphenylpropionic acid ester of formula (I).
As a purification method of 1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, Japanese Patent Publication No. 3-9134 discloses a recrystallization method from n-hexane. However, when this method is directly applied to the compound of formula (I), αβ crystal is obtained. αβ crystal, Cu
When subjected to X-ray diffraction using -Kα wavelength X-ray, a diffraction pattern as shown in FIG. 4 is shown.
【０００９】δ晶は、水溶性溶媒と水との混合物または
環状脂肪族炭化水素類を再結晶溶媒として用い、４０℃
以上で結晶を析出させるか、あるいは非水溶性溶媒と鎖
状脂肪族炭化水素類との混合物から再結晶させることに
よって得られ、その融点範囲は約１２４〜１２７℃であ
る。δ晶は、Cu−Ｋα波長のＸ線を用いたＸ線回折にか
けると、図３のような回折パターンを示す。The δ-crystal is a mixture of a water-soluble solvent and water or a cycloaliphatic hydrocarbon as a recrystallization solvent, and is used at 40 ° C.
It is obtained by precipitating crystals or recrystallizing from a mixture of a water-insoluble solvent and a chain aliphatic hydrocarbon, and the melting point range is about 124 to 127 ° C. The δ crystal shows a diffraction pattern as shown in FIG. 3 when subjected to X-ray diffraction using Cu-Kα wavelength X-rays.
【００１０】[0010]
【発明が解決しようとする課題】以上のような、従来知
られている式（Ｉ）のヒドロキシフェニルプロピオン酸
エステルの結晶形のうち、γ晶はガラス状であり、また
αβ晶およびδ晶は微粉末であって、いずれも工業的ス
ケールで製造する際の濾過性、あるいは製品取扱い時の
流動性が悪く、計量性、輸送性、作業性などの面で必ず
しも満足できるものではなかった。Among the crystal forms of the conventionally known hydroxyphenylpropionic acid ester of the formula (I) as described above, the γ crystal is glassy, and the αβ crystal and the δ crystal are It was a fine powder, and all of them had poor filterability during production on an industrial scale or poor fluidity during product handling, and were not necessarily satisfactory in terms of weighing property, transport property, workability and the like.
【００１１】そこでさらに研究を重ねた結果、特定の再
結晶溶媒を組み合わせることによって、従来のものとは
まったく異なる結晶構造を有する式（Ｉ）のヒドロキシ
フェニルプロピオン酸エステルが得られ、しかもこのよ
うな新規な結晶構造を有するヒドロキシフェニルプロピ
オン酸エステルは、製造時の濾過性が改善され、さらに
は製品の嵩比重が大きく、また流動性などの作業性にも
優れることを見出し、本発明に至った。As a result of further studies, hydroxyphenylpropionic acid ester of the formula (I) having a crystal structure completely different from the conventional one was obtained by combining a specific recrystallization solvent, and The hydroxyphenylpropionic acid ester having a novel crystal structure was found to have improved filterability during production, large bulk specific gravity of the product, and excellent workability such as fluidity, leading to the present invention. .
【００１２】[0012]
【課題を解決するための手段】すなわち本発明は、Cu−
Ｋα波長のＸ線を用いたＸ線回折測定により、回折角２
θ＝７.9°に鋭いＸ線回折ピークを示す結晶構造を有す
る前記式（Ｉ）で示されるヒドロキシフェニルプロピオ
ン酸エステルを提供するものである。That is, the present invention provides Cu-
By the X-ray diffraction measurement using the X-ray of Kα wavelength, the diffraction angle of 2
The present invention provides a hydroxyphenylpropionic acid ester represented by the above formula (I) having a crystal structure showing a sharp X-ray diffraction peak at θ = 7.9 °.
【００１３】本発明による新規な結晶構造（以下、ε晶
と呼ぶ）を有する前記式（Ｉ）のヒドロキシフェニルプ
ロピオン酸エステルは、Cu−Ｋα波長のＸ線を用いたＸ
線回折測定により、図１のような回折パターンを示す。
図１の回折パターンを詳しく解析すると表１のようにな
る。The hydroxyphenylpropionic acid ester of the above formula (I) having a novel crystal structure (hereinafter referred to as ε crystal) according to the present invention is X-ray using X-ray of Cu-Kα wavelength.
A line diffraction measurement shows a diffraction pattern as shown in FIG.
Table 1 shows a detailed analysis of the diffraction pattern of FIG.
【００１４】[0014]
【表１】 [Table 1]
【００１５】こうした本発明によるε晶の融点は、純度
が極めて高ければ約１１６〜１１９℃の範囲にあるが、
通常の化合物と同様、純度低下や他の結晶形との混合に
よって、上記の融点範囲より若干低い、またはより広い
融点範囲を示すことがある。その融点範囲は一概にいえ
ないが、概ね１１０〜１２４℃の範囲に入る。The melting point of the ε crystal according to the present invention is in the range of about 116 to 119 ° C. if the purity is extremely high.
Like ordinary compounds, the melting point range may be slightly lower or wider than the above melting point range due to deterioration of purity or mixing with other crystalline forms. Although its melting point range cannot be generally specified, it falls within a range of about 110 to 124 ° C.
【００１６】また本発明のε晶は、表１および図１に示
したようなCu−Ｋα波長のＸ線を用いたＸ線回折パター
ンのうち、特に２θ＝７.9°にある鋭い回折ピークによ
り、容易に従来公知のδ晶、αβ晶およびγ晶と区別す
ることができる。すなわち、δ晶は特開昭 62-149679号
公報に記載されまた図３に示すように、２θ＝４.2°お
よび２θ＝１０.6°に鋭い回折ピークを示し、αβ晶は
特開昭 62-149680号公報に記載されまた図４に示すよう
に、２θ＝２.8°、２θ＝８.7°および２θ＝１１.7°
に鋭い回折ピークを示すが、いずれも２θ＝７.9°には
回折ピークはみられない。一方γ晶は、図５に示すよう
に固有の回折ピークを示さない。さらに本発明のε晶
は、δ晶やαβ晶にみられる２θ＝３〜４°付近の回折
ピークがない点でも、δ晶やαβ晶と区別される。Further, the ε crystal of the present invention has a sharp diffraction peak at 2θ = 7.9 ° in the X-ray diffraction pattern using Cu-Kα wavelength X-rays as shown in Table 1 and FIG. Thus, it can be easily distinguished from the conventionally known δ crystal, αβ crystal, and γ crystal. That is, the δ crystal shows sharp diffraction peaks at 2θ = 4.2 ° and 2θ = 10.6 ° as described in JP-A-62-149679 and as shown in FIG. No. 62-149680 and as shown in FIG. 4, 2θ = 2.8 °, 2θ = 8.7 ° and 2θ = 11.7 °.
Shows a sharp diffraction peak at 2, but no diffraction peak is observed at 2θ = 7.9 °. On the other hand, the γ crystal does not show a unique diffraction peak as shown in FIG. Further, the ε crystal of the present invention is distinguished from the δ crystal and the αβ crystal in that there is no diffraction peak around 2θ = 3 to 4 ° found in the δ crystal and the αβ crystal.
【００１７】本発明によるε晶は、δ晶およびαβ晶に
比べて結晶が成長しやすく、その結果大きな結晶が得ら
れ、製造時の濾過性および製品取扱い時の輸送性、計量
性、作業性などが改善される。またε晶は、晶析操作の
際、反応によって生成する不純物の取り込みが少なく、
結果としてδ晶およびαβ晶より純度の高い製品を得る
ことができる。The ε crystal according to the present invention is more likely to grow than the δ crystal and the αβ crystal, and as a result, a large crystal is obtained, and the filterability during manufacturing and the transportability, metering property, and workability during product handling are improved. Etc. are improved. Further, the ε crystal has a small uptake of impurities generated by the reaction during the crystallization operation,
As a result, a product having a higher purity than the δ crystal and the αβ crystal can be obtained.
【００１８】ε晶はまた、有機溶媒に対して、δ晶およ
びαβ晶より低い溶解度を示し、さらには反応によって
生成する不純物との相互溶解度も低いため、高い収率で
得られる。表２は、ε晶およびδ晶の各種有機溶媒に対
する溶解度を２０℃で測定した結果を示している。The ε crystal also has a lower solubility in organic solvents than the δ crystal and the αβ crystal, and further has a low mutual solubility with impurities produced by the reaction, so that it can be obtained in a high yield. Table 2 shows the results of measuring the solubility of the ε crystal and the δ crystal in various organic solvents at 20 ° C.
【００１９】[0019]
【表２】 [Table 2]
【００２０】さらにε晶は、従来の結晶であるαβ晶や
δ晶に比べて吸湿性が小さいため、ポリウレタン製造時
など、水分の影響を受けやすい用途に対しても、再乾
燥、防湿包装といった追加操作を加えることなく、簡便
に好適に用いることができる。表３は、ε晶およびδ晶
について、製品粉末を室温、相対湿度１００％の雰囲気
に一定期間暴露し、各期間暴露後の水分量をカールフィ
シャー法にて求めた結果を示している。Further, since the ε crystal has a smaller hygroscopicity than the conventional crystals of αβ crystal and δ crystal, it is suitable for re-drying and moisture-proof packaging even for applications such as polyurethane production which are easily affected by moisture. It can be conveniently and suitably used without adding an additional operation. Table 3 shows the results for the ε crystal and the δ crystal, in which the product powder was exposed to an atmosphere of room temperature and 100% relative humidity for a certain period of time, and the water content after each period of exposure was determined by the Karl Fischer method.
【００２１】[0021]
【表３】 [Table 3]
【００２２】このように、本発明によるε晶は種々の優
れた特性を有し、こうした特性は、従来技術からはまっ
たく予測できないものであった。As described above, the ε crystal according to the present invention has various excellent characteristics, and such characteristics were completely unpredictable from the prior art.
【００２３】かかるε晶は、式（Ｉ）で示されるヒドロ
キシフェニルプロピオン酸エステルを、炭素数６〜１２
の芳香族炭化水素類から選ばれる第１の溶媒と、炭素数
６〜１０の脂肪族炭化水素類から選ばれる第２の溶媒と
の混合溶媒に溶かし、次いで種晶を投入して再結晶を行
うことにより、得ることができる。この場合、第１の溶
媒と２の溶媒との割合、あるいはヒドロキシフェニルプ
ロピオン酸エステルに対する混合溶媒の量や晶析温度な
どの晶析条件により、その他の結晶形との混合物になっ
たり、製品純度低下を招くことがある。そこで、式
（Ｉ）で示されるヒドロキシフェニルプロピオン酸エス
テルを、前記第１の溶媒および前記第２の溶媒に加え
て、さらに水溶性の有機溶媒から選ばれる第３の溶媒を
用いた混合溶媒に溶かし、次いで種晶を用いて結晶化を
行う方法を採用すれば、高品質の製品を高い収率で得る
ことができる。The ε crystal is prepared by converting the hydroxyphenylpropionic acid ester represented by the formula (I) into 6 to 12 carbon atoms.
Is dissolved in a mixed solvent of a first solvent selected from the aromatic hydrocarbons and a second solvent selected from the aliphatic hydrocarbons having 6 to 10 carbon atoms, and then seed crystals are added to recrystallize the solvent. It can be obtained by carrying out. In this case, depending on the ratio of the first solvent and the second solvent, or the crystallization conditions such as the amount of the mixed solvent with respect to the hydroxyphenylpropionic acid ester and the crystallization temperature, a mixture with other crystal forms or a product purity may be obtained. It may cause a decrease. Therefore, the hydroxyphenylpropionic acid ester represented by the formula (I) is added to the first solvent and the second solvent to prepare a mixed solvent using a third solvent selected from water-soluble organic solvents. If a method of melting and then crystallizing using a seed crystal is adopted, a high quality product can be obtained in a high yield.
【００２４】第１の溶媒である炭素数６〜１２の芳香族
炭化水素類としては、ベンゼン、トルエン、エチルベン
ゼン、キシレン、クメン、シメン、クロルベンゼンなど
を挙げることができ、なかでも、トルエンおよびキシレ
ンが好ましく用いられる。一方、第２の溶媒である炭素
数６〜１２の脂肪族炭化水素類としては、ｎ−ヘキサ
ン、ｎ−ヘプタン、ｎ−オクタン、ｎ−デカンなどを挙
げることができ、なかでも、ｎ−ヘキサンおよびｎ−ヘ
プタンが特に好ましい。Examples of the aromatic hydrocarbons having 6 to 12 carbon atoms as the first solvent include benzene, toluene, ethylbenzene, xylene, cumene, cymene and chlorobenzene, and among them, toluene and xylene are preferable. Is preferably used. On the other hand, examples of the aliphatic hydrocarbon having 6 to 12 carbon atoms which is the second solvent include n-hexane, n-heptane, n-octane and n-decane, and among them, n-hexane. And n-heptane are particularly preferred.
【００２５】また、第３の溶媒である水溶性の有機溶媒
を用いる場合、かかる水溶性の溶媒としては、アルコー
ル類、グリコール類、脂肪族ケトン類、脂肪族ニトリル
類、環状脂肪族エーテル類、アミド類、および３級アミ
ン類などが挙げられ、これらのなかでも、特にアルコー
ル類が好ましく用いられる。アルコール類としては、炭
素数１〜８のもの、例えばメタノール、エタノール、ｎ
−プロパノール、イソプロパノール、ｎ−ブタノール、
イソブタノール、ｎ−ヘキサノール、２−エチルヘキサ
ノールなどが挙げられ、なかでもメタノールが特に好ま
しい。グリコール類としては炭素数２〜６のものが好ま
しく、例えばエチレングリコール、トリメチレングリコ
ール、ジエチレングリコール、トリエチレングリコール
などが挙げられる。脂肪族ケトン類としては、例えばア
セトン、メチルエチルケトン、ジエチルケトン、メチル
イソブチルケトンなどが挙げられ、脂肪族ニトリル類と
しては、例えばアセトニトリル、プロピオニトリルなど
を挙げることができる。環状脂肪族エーテル類として
は、例えば１，４−ジオキサン、テトラヒドロフランな
どが挙げられ、 アミド類としては、例えばＮ，Ｎ−ジ
メチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、
Ｎ−メチル−２−ピロリドンなどが挙げられ、また３級
アミン類としては、例えばトリエチルアミン、ピリジン
などが挙げられる。When a water-soluble organic solvent which is the third solvent is used, examples of the water-soluble solvent include alcohols, glycols, aliphatic ketones, aliphatic nitriles, cycloaliphatic ethers, Examples thereof include amides and tertiary amines. Among these, alcohols are particularly preferably used. Alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, n
-Propanol, isopropanol, n-butanol,
Examples thereof include isobutanol, n-hexanol, and 2-ethylhexanol. Among them, methanol is particularly preferable. As the glycols, those having 2 to 6 carbon atoms are preferable, and examples thereof include ethylene glycol, trimethylene glycol, diethylene glycol, and triethylene glycol. Examples of the aliphatic ketones include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone, and examples of the aliphatic nitriles include acetonitrile and propionitrile. Examples of the cyclic aliphatic ethers include 1,4-dioxane and tetrahydrofuran, and examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide,
Examples thereof include N-methyl-2-pyrrolidone, and examples of the tertiary amines include triethylamine and pyridine.
【００２６】混合溶媒を構成する２種の溶媒あるいは３
種の溶媒のうち、第１の溶媒である芳香族炭化水素類お
よび第３の溶媒である水溶性の有機溶媒は通常、式
（Ｉ）で示されるヒドロキシフェニルプルピオン酸エス
テルの晶析過程における溶解剤として作用し、精製効果
を向上させたりする。また第２の溶媒である脂肪族炭化
水素類は、晶析過程において、ヒドロキシフェニルプロ
ピオン酸エステルの第１の溶媒に対する溶解度および結
晶の析出時間を制御し、収率を向上させたりする。第３
の溶媒である水溶性の有機溶媒を用いる場合、この水溶
性溶媒は、第２の溶媒との相溶性が比較的悪いため、第
１の溶媒および第２の溶媒と併用される。第３の溶媒で
ある水溶性溶媒は通常、ヒドロキシフェニルプルピオン
酸エステルを溶解している第１の溶媒に、第２の溶媒と
ともに添加されるが、第１の溶媒と第３の溶媒の混合溶
媒としてヒドロキシフェニルプルピオン酸エステルを溶
解し、そこに第２の溶媒を添加することもできる。Two types of solvents or 3 constituting the mixed solvent
Of the seed solvents, the first solvent, an aromatic hydrocarbon, and the third solvent, a water-soluble organic solvent, are usually used in the crystallization process of the hydroxyphenylpurupionate ester represented by the formula (I). It acts as a solubilizer and improves the purification effect. Further, the aliphatic hydrocarbons as the second solvent control the solubility of the hydroxyphenylpropionic acid ester in the first solvent and the crystal precipitation time in the crystallization process to improve the yield. Third
When a water-soluble organic solvent that is the solvent of (1) is used, this water-soluble solvent is used in combination with the first solvent and the second solvent because the compatibility with the second solvent is relatively poor. The water-soluble solvent that is the third solvent is usually added to the first solvent in which the hydroxyphenylpurpionate ester is dissolved together with the second solvent, but the mixture of the first solvent and the third solvent is added. It is also possible to dissolve hydroxyphenylpurupionate as a solvent and add the second solvent thereto.
【００２７】晶析操作においては、ヒドロキシフェニル
プロピオン酸エステルの重量を基準として、第１の溶媒
を５０〜１５０重量％程度用いるのが好ましい。また第
２の溶媒は、第１の溶媒の重量を基準として０.8〜２.5
重量倍程度用いるのが好ましい。これらの範囲をはずれ
ると、目的物の品質や収率を低下させたり、他の結晶形
が得られたりする。また晶析装置へのスケーリングをも
たらすこともあるので好ましくない。第３の溶媒を用い
る場合は、第１の溶媒の重量を基準として０.2〜１０重
量％程度用いるのが好ましい。種晶の結晶形はε晶が好
ましいが、δ晶を種晶とすることもできる。In the crystallization operation, it is preferable to use about 50 to 150% by weight of the first solvent, based on the weight of hydroxyphenylpropionic acid ester. Also, the second solvent is 0.8 to 2.5 based on the weight of the first solvent.
It is preferable to use about twice the weight. If it deviates from these ranges, the quality and yield of the target product may be reduced, and other crystal forms may be obtained. In addition, it may cause scaling to the crystallizer, which is not preferable. When the third solvent is used, it is preferable to use about 0.2 to 10% by weight based on the weight of the first solvent. The crystal form of the seed crystal is preferably ε crystal, but δ crystal can also be used as the seed crystal.
【００２８】晶析操作は通常、まず第１の溶媒を単独で
用い、沸点またはそれ以下の温度にて、式（Ｉ）で示さ
れるヒドロキシフェニルプルピオン酸エステルの粗生成
物を完全に溶解させ、その後第２の溶媒を添加し、ある
いは第２の溶媒および第３の溶媒を添加し、３０〜７０
℃の温度範囲でさらに結晶の核となる種晶を加えて、結
晶析出が行われる。そののち冷却して、析出が完全に行
われるようにする。また場合によっては、第１の溶媒お
よび第２の溶媒を同時に用い、あるいは第１の溶媒、第
２の溶媒および第３の溶媒を同時に用い、そこに粗生成
物を溶解させて晶析する方法をとることもできる。析出
した結晶は、濾過などによって母液から分離し、洗浄、
乾燥することによって、単離されたε晶とすることがで
きる。The crystallization operation is usually carried out by first using the first solvent alone to completely dissolve the crude product of the hydroxyphenylpurupionic acid ester represented by the formula (I) at the boiling point or lower. , Then adding a second solvent, or adding a second solvent and a third solvent, 30-70
Crystal precipitation is carried out by further adding a seed crystal which becomes a nucleus of the crystal in the temperature range of ° C. Then, it is cooled so that the precipitation is completely performed. In some cases, the first solvent and the second solvent are used at the same time, or the first solvent, the second solvent and the third solvent are used at the same time, and the crude product is dissolved therein for crystallization. Can also be taken. The precipitated crystals are separated from the mother liquor by filtration or the like, washed,
The isolated ε crystal can be obtained by drying.
【００２９】この晶析操作において、ε晶を得るには結
晶化をゆるやかに行うことが必要であり、また混合溶媒
の割合や混合溶媒の量、さらには結晶化温度や種晶の結
晶形も、得られる結晶の形に影響する。上記の操作を短
時間で行った場合、δ晶あるいはδ晶とε晶の混合物と
なり、さらには結晶の凝集が著しくなって、純度や色相
などの製品品質が低下する傾向にある。In this crystallization operation, in order to obtain ε crystal, it is necessary to perform crystallization slowly, and the ratio of the mixed solvent and the amount of the mixed solvent, the crystallization temperature and the crystal form of the seed crystal are also determined. , Affect the shape of the crystals obtained. When the above operation is carried out in a short time, a δ crystal or a mixture of δ crystal and ε crystal is formed, and further crystal agglomeration becomes remarkable, and product quality such as purity and hue tends to be deteriorated.
【００３０】かくして、本発明のε晶は、特定の溶媒を
用いることにより得られ、高品質でしかも高嵩比重の流
動性に優れた結晶である。Thus, the ε crystal of the present invention is a crystal which is obtained by using a specific solvent and has a high quality and a high bulk specific gravity and excellent fluidity.
【００３１】[0031]
【実施例】次に、具体的な参考例および実施例を示し
て、本発明をさらに詳細に説明するが、本発明はこれら
によって限定されるものではない。なお、例中にある％
は、特にことわらないかぎり重量基準である。EXAMPLES Next, the present invention will be described in more detail by showing specific reference examples and examples, but the present invention is not limited to these. In addition,% in the example
Is weight basis unless otherwise specified.
【００３２】参考例１ 理論段数６段でスルーザーパッキンを充填した内径２０
mmの精留塔、攪拌装置および温度計を備えた２リットル
四つ口フラスコに、３−（３−ｔ−ブチル−４−ヒドロ
キシ−５−メチルフェニル）プロピオン酸メチル８６
３.4ｇ（３.4５モル）、 ３，９−ビス（２−ヒドロキ
シ−１，１−ジメチルエチル）−２，４，８，１０−テ
トラオキサスピロ〔５・５〕ウンデカン４５６.6ｇ
（１.5モル）、およびトルエン７５０ｇを仕込んだ。攪
拌下、徐々に１００mmHgまで減圧してから昇温し、精留
塔上部の受器に６００ｇのトルエンの留出と受器からの
トルエンの戻りを確認したあと、約９０℃、１００mmHg
の条件で１時間還流させた。次いで窒素ガスを供給して
大気圧に戻し、リチウムアミド３.4５ｇ（０.1５モル）
をメタノール５１.5ｇに溶解したものを常圧で加えた。
常圧で徐々に昇温し、生成するメタノールを留去しつ
つ、１４０℃で６時間保温、還流し、反応を完結させ
た。Reference Example 1 Inner diameter 20 filled with sruzer packing with 6 theoretical plates
In a 2-liter four-necked flask equipped with a mm rectification column, a stirrer and a thermometer, methyl 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate 86
3.4 g (3.45 mol), 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane 456.6 g
(1.5 mol) and 750 g of toluene were charged. After stirring, the pressure was gradually reduced to 100 mmHg and then the temperature was raised. After confirming that 600 g of toluene was distilled out and returned from the receiver in the upper part of the rectification column, it was heated to approximately 90 ° C and 100 mmHg.
The mixture was refluxed for 1 hour under the above conditions. Then, nitrogen gas was supplied to return to atmospheric pressure, and lithium amide 3.45 g (0.15 mol)
Dissolved in 51.5 g of methanol was added at normal pressure.
The temperature was gradually raised at normal pressure, and while the produced methanol was distilled off, the mixture was kept at 140 ° C. for 6 hours and refluxed to complete the reaction.
【００３３】反応終了後、少量のトルエンを加えて８５
℃まで冷却し、酢酸１２ｇ（０.2モル）にて中和後、水
洗して水層を分液除去した。次に、減圧下で有機層から
溶媒を完全に留去し、淡黄色飴状の蒸留残査１２６６ｇ
を得た。この蒸留残査には、３，９−ビス〔２−｛３−
（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニ
ル）プロピオニルオキシ｝−１，１−ジメチルエチル〕
−２，４，８，１０−テトラオキサスピロ〔５・５〕ウ
ンデカン８２.8％、原料である３−（３−ｔ−ブチル−
４−ヒドロキシ−５−メチルフェニル）プロピオン酸メ
チル８.1％、その他副反応物９.1％が含まれていること
を確認した。この飴状物は、Cu−Ｋα波長のＸ線回折に
より、図５に示す回折パターンを与えた。After completion of the reaction, a small amount of toluene was added to add 85
The mixture was cooled to 0 ° C., neutralized with 12 g (0.2 mol) of acetic acid, and washed with water to remove the aqueous layer. Next, the solvent was completely distilled off from the organic layer under reduced pressure, and 1266 g of a pale yellow candy-like distillation residue was obtained.
Got This distillation residue contained 3,9-bis [2- {3-
(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl]
-2,4,8,10-Tetraoxaspiro [5.5] undecane 82.8%, starting material 3- (3-t-butyl-)
It was confirmed that 8.1% of methyl 4-hydroxy-5-methylphenyl) propionate and 9.1% of other by-products were contained. This candy-like product gave the diffraction pattern shown in FIG. 5 by X-ray diffraction at a Cu-Kα wavelength.
【００３４】実施例１ 温度計、撹拌装置、冷却管および滴下装置を備えた反応
容器中にて、参考例１で得られた蒸留残査２００.0ｇを
１２０.0ｇのトルエンに８０℃で溶解させたのち、撹拌
下でｎ−ヘキサン２８０.0ｇを徐々に加え、そして５０
℃で、ε晶の種晶１.0ｇを投入した。次に、５０〜５５
℃の温度範囲で７時間保温して結晶を析出させ、さらに
２０℃まで徐々に冷却し、得られた結晶を同温度にて濾
過し、ｎ−ヘキサンで洗浄した。その後減圧下、６５℃
で乾燥して、融点１１５〜１１８℃の白色結晶１６４.1
ｇを得た。Example 1 In a reaction vessel equipped with a thermometer, a stirrer, a condenser and a dropping device, 20.0 g of the distillation residue obtained in Reference Example 1 was dissolved in 120.0 g of toluene at 80 ° C. After that, 280.0 g of n-hexane was gradually added under stirring, and 50
At 0 ° C., 1.0 g of ε crystal seed crystal was added. Next, 50-55
Crystals were precipitated by keeping the temperature in the temperature range of 7 ° C for 7 hours and then gradually cooled to 20 ° C. The obtained crystals were filtered at the same temperature and washed with n-hexane. Then, under reduced pressure, 65 ℃
White crystals 164.1 having a melting point of 115-118 ° C.
g was obtained.
【００３５】この白色結晶を分析したところ、目的物の
３，９−ビス〔２−｛３−（３−ｔ−ブチル−４−ヒド
ロキシ−５−メチルフェニル）プロピオニルオキシ｝−
１，１−ジメチルエチル〕−２，４，８，１０−テトラ
オキサスピロ〔５・５〕ウンデカンが９８.4％含まれて
おり、また３−（３−ｔ−ブチル−４−ヒドロキシ−５
−メチルフェニル）プロピオン酸メチルおよびその他副
反応生成物が、それぞれ０.3％および１.3％含まれてい
ることが認められた。この白色結晶について、Cu−Ｋα
波長によるＸ線回折測定を行ったところ、図１に示すＸ
線回折パターンが得られ、回折角２θ＝７.9°に鋭いＸ
線回折ピークが認められた。この結晶の物性値を表４に
示す。Analysis of the white crystals revealed that the desired product, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy}-
It contains 98.4% of 1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, and 3- (3-t-butyl-4-hydroxy-5).
-Methylphenyl) methyl propionate and other side reaction products were found to be included at 0.3% and 1.3%, respectively. For this white crystal, Cu-Kα
When X-ray diffraction measurement by wavelength was performed, X-ray shown in FIG.
A linear diffraction pattern was obtained, and a sharp X was observed at a diffraction angle 2θ = 7.9 °.
A line diffraction peak was observed. The physical properties of this crystal are shown in Table 4.
【００３６】実施例２ 上記実施例１で用いたのと同じ反応容器中にて、参考例
１で得られた蒸留残査２００.0ｇを１２０.0ｇのキシレ
ンに８０℃で溶解させたのち、攪拌下でｎ−ヘプタン２
００.0ｇおよびメタノール２.0ｇを徐々に加え、そして
５０℃で、ε晶の種晶１.0ｇを投入した。次に、５０〜
５５℃の温度範囲で１２時間保温して結晶を析出させ、
さらに２０℃まで徐々に冷却し、得られた結晶を同温度
にて濾過し、ｎ−ヘプタンで洗浄した。その後減圧下、
６５℃で乾燥して、融点１１５〜１１８℃の白色結晶１
５８.0ｇを得た。Example 2 In the same reaction vessel used in Example 1 above, 20.0 g of the distillation residue obtained in Reference Example 1 was dissolved in 120.0 g of xylene at 80 ° C. N-heptane 2 under stirring
0.0 g and 2.0 g of methanol were gradually added, and at 50 ° C., 1.0 g of seed crystal of ε crystal was added. Next, 50-
Incubate for 12 hours in the temperature range of 55 ° C to precipitate crystals,
After further cooling to 20 ° C., the obtained crystals were filtered at the same temperature and washed with n-heptane. Then under reduced pressure,
White crystal 1 having a melting point of 115 to 118 ° C. when dried at 65 ° C.
58.0 g was obtained.
【００３７】この白色結晶を分析したところ、目的物の
３，９−ビス〔２−｛３−（３−ｔ−ブチル−４−ヒド
ロキシ−５−メチルフェニル）プロピオニルオキシ｝−
１，１−ジメチルエチル〕−２，４，８，１０−テトラ
オキサスピロ〔５・５〕ウンデカンが９８.5％含まれて
おり、また３−（３−ｔ−ブチル−４−ヒドロキシ−５
−メチルフェニル）プロピオン酸メチルおよびその他副
反応生成物が、それぞれ０.3％および１.2％含まれてい
ることが認められた。この白色結晶について、Cu−Ｋα
波長によるＸ線回折測定を行ったところ、図１と同様な
Ｘ線回折パターンが得られ、回折角２θ＝７.9°に鋭い
Ｘ線回折ピークが認められた。この結晶の物性値を表４
に示す。Analysis of the white crystals revealed that the desired product, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy}-
It contains 98.5% of 1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, and 3- (3-t-butyl-4-hydroxy-5).
-Methylphenyl) methyl propionate and other side reaction products were found to be included at 0.3% and 1.2%, respectively. For this white crystal, Cu-Kα
When the X-ray diffraction measurement by wavelength was performed, the same X-ray diffraction pattern as in FIG. 1 was obtained, and a sharp X-ray diffraction peak was recognized at the diffraction angle 2θ = 7.9 °. Physical properties of this crystal are shown in Table 4.
Shown in.
【００３８】実施例３ 実施例２で得られた結晶５０.0ｇを、トルエン４０.0ｇ
とメタノール１.0ｇの混合溶媒に６５℃で溶解させたの
ち、撹拌下でｎ−ヘキサン６０.0ｇを加え、そして５０
℃で、δ晶の種晶０.2５ｇを投入し、５０〜５５℃の温
度範囲で１２時間保温した。その後は実施例２と同様の
操作を行い、融点１１６〜１１９℃の白色結晶４７.2ｇ
を得た。この結晶について、Cu−Ｋα波長によるＸ線回
折を行ったところ、図１と同様なＸ線回折パターンが得
られた。この結晶を得るまでの成績および物性値測定結
果は表４に示した。Example 3 50.0 g of the crystals obtained in Example 2 were mixed with 40.0 g of toluene.
After dissolving in a mixed solvent of 1.0 g of methanol and 65 g of methanol at 65 ° C., 60.0 g of n-hexane was added with stirring, and 50
At 25 ° C., 0.25 g of δ crystal seed crystals were added, and the temperature was kept at 50 to 55 ° C. for 12 hours. Thereafter, the same operation as in Example 2 was performed, and 47.2 g of white crystals having a melting point of 116 to 119 ° C.
Got When this crystal was subjected to X-ray diffraction at a Cu-Kα wavelength, an X-ray diffraction pattern similar to that shown in FIG. 1 was obtained. Table 4 shows the results until the crystals were obtained and the results of measurement of physical properties.
【００３９】比較例１ 実施例１におけるε晶の種晶の代わりにδ晶の種晶を用
いた以外は、同様の操作を行い、融点１２１〜１２４℃
の白色結晶１６８.5ｇを得た。この白色結晶について、
Cu−Ｋα波長によるＸ線回折測定を行ったところ、図２
に示すＸ線回折パターンが得られた。この結晶を得るま
での成績および物性値測定結果は表５に示した。Comparative Example 1 The same operation was performed except that the δ crystal seed crystal was used in place of the ε crystal seed crystal in Example 1, and the melting point was 121 to 124 ° C.
168.5 g of white crystals of For this white crystal,
An X-ray diffraction measurement with Cu-Kα wavelength was carried out.
The X-ray diffraction pattern shown in was obtained. Table 5 shows the results until the crystals were obtained and the results of measurement of physical properties.
【００４０】比較例２ 実施例１におけるトルエンの代わりにメタノール３４
０.0ｇを用いて５０℃で溶解させ、またｎ−ヘキサンの
代わりに水６０.0ｇを用いた以外は、同様の操作を行
い、融点１２４〜１２７℃の白色結晶１６５.6ｇを得
た。この白色結晶について、Cu−Ｋα波長によるＸ線回
折測定を行ったところ、図３に示すＸ線回折パターンが
得られた。この結晶を得るまでの成績および物性値測定
結果は表５に示した。Comparative Example 2 Methanol 34 was used instead of toluene in Example 1.
16 g of white crystals having a melting point of 124 to 127 ° C. were obtained by the same operation except that 0.0 g was dissolved at 50 ° C., and 60.0 g of water was used instead of n-hexane. When this white crystal was subjected to X-ray diffraction measurement with a Cu-Kα wavelength, the X-ray diffraction pattern shown in FIG. 3 was obtained. Table 5 shows the results until the crystals were obtained and the results of measurement of physical properties.
【００４１】比較例３ 実施例１におけるトルエンとｎ−ヘキサンの混合溶媒の
代わりにｎ−ヘキサンのみを１０００ｇ用い、７０℃で
溶解させたのち３０℃まで冷却し、種晶１.0ｇを投入し
たあと、同温度で７時間保温し結晶を析出させた以外
は、同様の操作を行い、融点９３〜１０１℃の淡黄色結
晶１７０.9ｇを得た。この結晶について、Cu−Ｋα波長
によるＸ線回折測定を行ったところ、図４に示すＸ線回
折パターンが得られた。この結晶を得るまでの成績は表
５に示した。Comparative Example 3 1000 g of n-hexane alone was used instead of the mixed solvent of toluene and n-hexane in Example 1, dissolved at 70 ° C., cooled to 30 ° C., and 1.0 g of seed crystals were added. Then, the same operation was carried out except that the temperature was kept at the same temperature for 7 hours to precipitate crystals, to obtain 170.9 g of pale yellow crystals having a melting point of 93 to 101 ° C. When this crystal was subjected to X-ray diffraction measurement with a Cu-Kα wavelength, the X-ray diffraction pattern shown in FIG. 4 was obtained. The results of obtaining the crystals are shown in Table 5.
【００４２】[0042]
【表４】 [Table 4]
【００４３】[0043]
【表５】 [Table 5]
【００４４】[0044]
【発明の効果】本発明は、従来まったく知られていなか
った新規な結晶構造（ε晶）を有する式（Ｉ）で示され
るヒドロキシフェニルプロピオン酸エステルを提供す
る。そしてこのε晶は、高品質であり、また大きな結晶
となるので製造時の濾過性に優れるほか、嵩比重が大き
く、流動性に優れることから、工業的に極めて有用な結
晶形である。INDUSTRIAL APPLICABILITY The present invention provides a hydroxyphenylpropionic acid ester represented by the formula (I) having a novel crystal structure (ε crystal) which has never been known. The ε crystal is a crystal form that is industrially extremely useful because it has a high quality and is a large crystal, and thus it has excellent filterability during production and has a large bulk specific gravity and excellent fluidity.
【図１】実施例１で得た本発明による結晶形を持つ化合
物（ε晶）のＸ線回折パターンである。FIG. 1 is an X-ray diffraction pattern of the compound having a crystal form according to the present invention (ε crystal) obtained in Example 1.
【図２】比較例１で得た結晶（δε晶）のＸ線回折パタ
ーンである。2 is an X-ray diffraction pattern of the crystal (δε crystal) obtained in Comparative Example 1. FIG.
【図３】比較例２で得た結晶（δ晶）のＸ線回折パター
ンである。FIG. 3 is an X-ray diffraction pattern of the crystal (δ crystal) obtained in Comparative Example 2.
【図４】比較例３で得た結晶（αβ晶）のＸ線回折パタ
ーンである。FIG. 4 is an X-ray diffraction pattern of the crystal (αβ crystal) obtained in Comparative Example 3.
【図５】参考例１で得た飴状物質（γ晶）のＸ線回折パ
ターンである。5 is an X-ray diffraction pattern of the candy-like substance (γ crystal) obtained in Reference Example 1. FIG.
Claims (1)
により、回折角２θ＝７.9°に鋭いＸ線回折ピークを示
す結晶構造を有する３，９−ビス〔２−｛３−（３−ｔ
−ブチル−４−ヒドロキシ−５−メチルフェニル）プロ
ピオニルオキシ｝−１，１−ジメチルエチル〕−２，
４，８，１０−テトラオキサスピロ〔５・５〕ウンデカ
ン。1. A 9,9-bis [2- {having a crystal structure showing a sharp X-ray diffraction peak at a diffraction angle 2θ = 7.9 ° by X-ray diffraction measurement using Cu-Kα wavelength X-rays. 3- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,
4,8,10-Tetraoxaspiro [5.5] undecane.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5089737A JP2906909B2 (en) | 1992-07-23 | 1993-04-16 | Hydroxyphenylpropionate with a novel crystal structure |
| US08/087,866 US5338869A (en) | 1992-07-23 | 1993-07-09 | Hydroxyphenylpropionic ester having novel crystal structure |
| CA002100285A CA2100285C (en) | 1992-07-23 | 1993-07-12 | Hydroxyphenylpropionic ester having novel crystal structure |
| DE69306694T DE69306694T2 (en) | 1992-07-23 | 1993-07-13 | Hydroxyphenylpropionic acid ester crystals and their preparation |
| EP93305473A EP0583879B1 (en) | 1992-07-23 | 1993-07-13 | Hydroxyphenylpropionic ester crystals and their production |
| TW082105756A TW295586B (en) | 1992-07-23 | 1993-07-20 | |
| KR1019930013877A KR100292669B1 (en) | 1992-07-23 | 1993-07-22 | Hydroxyphenylpropionate Ester with Novel Crystal Structure |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-196870 | 1992-07-23 | ||
| JP19687092 | 1992-07-23 | ||
| JP5089737A JP2906909B2 (en) | 1992-07-23 | 1993-04-16 | Hydroxyphenylpropionate with a novel crystal structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0687860A true JPH0687860A (en) | 1994-03-29 |
| JP2906909B2 JP2906909B2 (en) | 1999-06-21 |
Family
ID=26431142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5089737A Expired - Fee Related JP2906909B2 (en) | 1992-07-23 | 1993-04-16 | Hydroxyphenylpropionate with a novel crystal structure |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5338869A (en) |
| EP (1) | EP0583879B1 (en) |
| JP (1) | JP2906909B2 (en) |
| KR (1) | KR100292669B1 (en) |
| CA (1) | CA2100285C (en) |
| DE (1) | DE69306694T2 (en) |
| TW (1) | TW295586B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005306858A (en) * | 2004-03-23 | 2005-11-04 | Sumitomo Chemical Co Ltd | Method for producing hydroxyphenylpropionic acid ester |
| JP2011251980A (en) * | 2004-03-23 | 2011-12-15 | Sumitomo Chemical Co Ltd | Method for producing hydroxyphenylpropionic acid ester |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925826A (en) * | 1982-08-04 | 1984-02-09 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin composition |
| JPS59231089A (en) * | 1983-06-14 | 1984-12-25 | Yoshitomi Pharmaceut Ind Ltd | Tetraoxaspiro(5-5)undecane derivative and organic material stabilizer composed of said compound |
| JPS60197747A (en) * | 1984-03-19 | 1985-10-07 | Sumitomo Chem Co Ltd | Stabilizer for synthetic resin |
| JPH0739419B2 (en) * | 1985-06-21 | 1995-05-01 | 住友化学工業株式会社 | Hydroxyphenylpropionate having a novel crystal structure and method for producing the same |
| US4769479A (en) * | 1985-06-21 | 1988-09-06 | Sumitomo Chemical Company, Limited | Hydroxyphenylpropionic acid ester with novel crystalline structure and production thereof |
-
1993
- 1993-04-16 JP JP5089737A patent/JP2906909B2/en not_active Expired - Fee Related
- 1993-07-09 US US08/087,866 patent/US5338869A/en not_active Expired - Lifetime
- 1993-07-12 CA CA002100285A patent/CA2100285C/en not_active Expired - Lifetime
- 1993-07-13 EP EP93305473A patent/EP0583879B1/en not_active Expired - Lifetime
- 1993-07-13 DE DE69306694T patent/DE69306694T2/en not_active Expired - Lifetime
- 1993-07-20 TW TW082105756A patent/TW295586B/zh not_active IP Right Cessation
- 1993-07-22 KR KR1019930013877A patent/KR100292669B1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005306858A (en) * | 2004-03-23 | 2005-11-04 | Sumitomo Chemical Co Ltd | Method for producing hydroxyphenylpropionic acid ester |
| JP2011251980A (en) * | 2004-03-23 | 2011-12-15 | Sumitomo Chemical Co Ltd | Method for producing hydroxyphenylpropionic acid ester |
| JP2015157853A (en) * | 2004-03-23 | 2015-09-03 | 住友化学株式会社 | Granules of hydroxyphenylpropionic acid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100292669B1 (en) | 2001-09-17 |
| EP0583879B1 (en) | 1996-12-18 |
| CA2100285A1 (en) | 1994-01-24 |
| DE69306694D1 (en) | 1997-01-30 |
| DE69306694T2 (en) | 1997-06-05 |
| CA2100285C (en) | 2004-03-16 |
| US5338869A (en) | 1994-08-16 |
| EP0583879A3 (en) | 1995-01-04 |
| JP2906909B2 (en) | 1999-06-21 |
| TW295586B (en) | 1997-01-11 |
| EP0583879A2 (en) | 1994-02-23 |
| KR940002247A (en) | 1994-02-17 |
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